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Scope and Limitations of the Application of Heterogeneous Enantioselective Catalysts

  • Chapter
Chiral Reactions in Heterogeneous Catalysis

Summary

The emphasis of this overview is placed on the synthetic potential and relevant characteristics of three classes of synthetic heterogeneous chiral catalysts (not covered are heterogeneous biocatalysts). i) Modified “classical” heterogeneous catalysts. The addition of chiral, low molecular weight modifiers to supported metal catalysts is most successful for preparing hydrogenation catalysts for α- and β-functionalized ketones. The main emphasis is on synthetic and technical applications but an update on mechanistic investigations and new systems is also given. The use of modified metal oxides is summarized. So far, only modified pillared clays for the epoxidation of allylic alcohols and the oxidation of aryl sulfides are of synthetic interest. ii) Chiral polymers. Reviewed are the uses of natural and synthetic chiral polymers as catalysts and supports. A few interesting concepts are described even though the synthetic application is restricted to poly(aminoacids) as selective catalysts for the epoxidation of chalcones and a polymer supported dipeptide for the hydrocyanation of aldehydes. A short section describes enantioselective reactions in chiral liquid crystal and gels. iii) Immobilized metal complexes. The preparation of different types of immobilized analogs of effective homogeneous chiral catalysts is assessed in detail. Each type is illustrated with representative examples. Requirements are discussed that are thought to be decisive for their synthetic application. Immobilized catalysts with high enantioselectivity and satisfactory activity have been developed for several reaction types. Most work has been carried out in hydrogenation, hydroformylation and oxidation reactions.

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References

  1. For a discussion of the synthetic problems see D. Seebach, Angew. Chem. 102 (1990) 1363.

    Article  CAS  Google Scholar 

  2. For a discussion of the industrial problems see R.A. Sheldon, Chirotechnology, Marcel Decker, Inc., New York, 1993.

    Google Scholar 

  3. E. Kokufuta, Prog. Polym. Sci., 17 (1992) 647.

    Article  CAS  Google Scholar 

  4. H.U. Blaser and M. Müller, Stud. Surf. Sci. Catal. 59 (1991) 73.

    Article  Google Scholar 

  5. H.U. Blaser, Tetrahedron: Asymmetry 2 (1991) 843.

    Article  CAS  Google Scholar 

  6. G. Webb and P.B. Wells, Catal. Today 12 (1992) 319.

    Article  CAS  Google Scholar 

  7. A. Tai and T. Harada, in Y. Iwasawa (Ed.), Taylored Metal Catalysts, D. Reidel, Dordrecht, 1986, p. 265.

    Chapter  Google Scholar 

  8. A. Tai, M. Imaida, T. Oda and H. Watanabe, Chem. Lett. (1978) 61.

    Google Scholar 

  9. A. Tai, N. Morimoto, M. Yoshikawa, K. Uehara, T. Sugimura and T. Kikukawa, Agric. Biol. Chem. 54 (1990) 1753.

    Article  CAS  Google Scholar 

  10. M. Nakahata, M. Imaida, H. Ozaki, T. Harada and A. Tai, Bull. Chem. Soc. Jpn. 55 (1982) 2186.

    Article  CAS  Google Scholar 

  11. J. Bakos, I. Toth and L. Marko, J. Org. Chem. 46 (1981) 5427.

    Article  CAS  Google Scholar 

  12. Catalogue of Wako Pure Chemicals Industries (Osaka), 22. Edition, p. 471 and 547 (cited in ref. [6]).

    Google Scholar 

  13. E. Broger, Hoffmann-LaRoche, Basel, personal communication.

    Google Scholar 

  14. E.I. Klabunovskii, Kinet. Katal. 33 (1992) 292, English translation p. 233.

    CAS  Google Scholar 

  15. H. Brunner, K. Amberger, T. Wischert and J. Wiehl, Bull. Soc. Chim. Belg. 100 (1991) 571 and 585.

    CAS  Google Scholar 

  16. M.A. Keane and G. Webb, J. Catal. 136 (1992) 1.

    Article  CAS  Google Scholar 

  17. M.A. Keane and G. Webb, J. Mol. Catal. 73 (1992) 91.

    Article  CAS  Google Scholar 

  18. M.A. Keane, Catal. Lett. 19 (1993) 197.

    Article  CAS  Google Scholar 

  19. A. Tai, T. Kikukawa, T. Sugimura, Y. Inoue, S. Abe, T. Osawa and T. Harada, in “ New Frontiers in Catalysis. Proceedings, 10th International Congress on Catalysis, Budapest, 1992 ”, L. Guczi, F. Solymosi and P. Tetenyi, Eds., Akademiai Kiado, Budapest, 1993, p. 2443 and J. Chem. Soc., Chem. Commun. (1991), 795.

    Google Scholar 

  20. H.U. Blaser, H.P. Jalett, D.M. Monti, A. Baiker and J.T. Wehrli, Stud. Surf. Sci. Catal. 67 (1991) 147.

    Article  CAS  Google Scholar 

  21. G.H. Sedelmeier, H.U. Blaser and H.P. Jalett; 1986; EP 206'993, assigned to Ciba-Geigy AG.

    Google Scholar 

  22. H.U. Blaser, S.K. Boyer and U. Pittelkow, Tetrahedron: Asymmetry 2 (1991) 721.

    Article  CAS  Google Scholar 

  23. G. Bond, P.A. Meheux, A. Ibbotson and P.B. Wells, Catal. Today 10 (1991) 371.

    Article  CAS  Google Scholar 

  24. G. Bond, K.E. Simons, A. Ibbotson, P.B. Wells and D.A. Whan, Catal. Today 12 (1992) 421.

    Article  CAS  Google Scholar 

  25. K.E. Simons, A. Ibbotson and P.B. Wells, Spec. Publ. - R. Soc. Chem. 114 (Catalysis and Surface Characterization), p. 174 (1992).

    Google Scholar 

  26. H.U. Blaser, M. Garland and H.P. Jalett, to be published in J. Catal. 144 (1993).

    Google Scholar 

  27. R.L. Augustine, S.K. Tanielyan and L.K. Doyle, Tetrahedron: Asymmetry 4 (1993) 1803.

    Article  CAS  Google Scholar 

  28. J.L. Margitfalvi, B. Minder, E. Talas, L. Botz and A. Baiker, in “ New Frontiers in Catalysis. Proceedings, 10th International Congress on Catalysis, Budapest, 1992 ”, L. Guczi, F. Solymosi and P. Tetenyi, Eds., Akademiai Kiado, Budapest, 1993, p. 2471.

    Google Scholar 

  29. E. Talas, L. Botz, J.L. Margitfalvi, O. Sticher and A. Baiker, J. Planar Chromatogr. 5. (1992) 28.

    CAS  Google Scholar 

  30. K.E. Simons, P.A. Meheux, A. Ibbotson and P.B. Wells, in “ New Frontiers in Catalysis. Proceedings, 10th International Congress on Catalysis, Budapest, 1992 ”, L. Guczi, F. Solymosi and P. Tetenyi, Eds., Akademiai Kiado, Budapest, 1993, p. 2317.

    Google Scholar 

  31. O. Schwalm, B. Minder, J. Weber and A. Baiker, in “ Abstracts, 2nd G.M. Schwab Symposium, Berlin, 1993 ”. Poster 2.7.

    Google Scholar 

  32. J.L. Margitfalvi, B. Minder, A. Baiker, P. Skrabal and E. Talas, in “ Abstracts, Europacat-1, Montpellier, 1993 ”, p. 406.

    Google Scholar 

  33. H.U. Blaser and M. Müller, in “ Abstracts, Europacat-1, Montpellier, 1993 ”, p. 408.

    Google Scholar 

  34. S. Bhaduri, V.S. Darshane, K. Sharma and D. Mukesh, J. Chem. Soc., Chem. Commun. (1992) 1738.

    Google Scholar 

  35. H.U. Blaser, H.P. Jalett, D.M. Monti, J.F. Reber and J.T. Wehrli, Stud. Surf. Sci. Catal. 41 (1988) 153.

    Article  CAS  Google Scholar 

  36. W.A.H. Vermeer, A. Fulford, P. Johnston and P.B. Wells, J. Chem. Soc., Chem. Commun. (1993) 1053.

    Google Scholar 

  37. H.U. Blaser and H.P. Jalett, Stud. Surf. Sci. Catal. 78 (1993) 139.

    Article  CAS  Google Scholar 

  38. P. Gallezot, private communication and K. Nasar, P. Drognat Landre, F. Fache, M. Besson, D. Richard, P. Gallezot and M. Lemaire, in “ Abstracts, Europacat-1, Montpellier, 1993 ”, p. 390.

    Google Scholar 

  39. H. Yamashita, Bull. Chem. Soc. Jpn., 61 (1988) 1213.

    Article  CAS  Google Scholar 

  40. B.M. Choudary, V.L.K. Valli and A. Durga Prasad, J. Chem. Soc., Chem. Commun. (1990) 1186.

    Google Scholar 

  41. B.M. Choudary, S. Shobha Rani and N. Narender, Catal. Lett. 19 (1993) 299.

    Article  CAS  Google Scholar 

  42. R.M. Dessau, US 4'554'262 (11. Nov. 1985) and US 4'666'874 (19. May 1987), assigned to Mobil Oil Corp.

    Google Scholar 

  43. M.E. Davis, Acc. Chem. Res. 26 (1993) 111.

    Article  CAS  Google Scholar 

  44. B.M. Choudary and S. Shobha Rani, J. Mol. Catal. 75 (1992) L7.

    Article  CAS  Google Scholar 

  45. J.N. Armor, Appl. Catal.78 (1991) 141.

    Article  CAS  Google Scholar 

  46. K. Morihara, S. Kawasaki, M. Kofuji and T. Shimada, Bull. Chem. Soc. Jpn. 66 (1993) 906, and references cited therein.

    Article  CAS  Google Scholar 

  47. T. Moriguchi, Y. G. Guo, S. Yamamoto, Y. Matsubara, M. Yoshihara and T. Maeshima, Chem. Express 7 (1992) 625.

    CAS  Google Scholar 

  48. C. Cativiela, F. Figueras, J.M. Fraile, J.I. Garcia, J.A. Mayoral, E. Pires and A.J. Royo, in “ Abstracts, Europacat-1, Montpellier, 1993 ”, p. 395.

    Google Scholar 

  49. For a review see M. Aglietto, E. Chiellini, S. D'Antone, G. Ruggeri and R. Solaro, Pure & Appl. Chem. 60 (1988) 415.

    Article  Google Scholar 

  50. S. Itsuno, M. Sakakura and K. Ito, J. Org. Chem. 55 (1990) 6047.

    Article  CAS  Google Scholar 

  51. J. Boulahia, F. Carriere and H. Sekiguchi, Makromol. Chem. 192 (1991) 2969.

    Article  CAS  Google Scholar 

  52. J.A.N. Augustyn, B.C.B. Bezuidenhoudt and D. Ferreira, Tetrahedron 46 (1990) 2651.

    Article  CAS  Google Scholar 

  53. J.R. Flisak, P.G. Gassman, I. Lantos and W.L. Mendelson, EP 403' 252 (19. Dec. 1990), assigned to SmithKlien Beecham Corp. for the structure of the active compound see J.G. Gleason et al., J. Med. Chem. 30 (1987) 959.

    Article  Google Scholar 

  54. A. Hanabusa, J. Ichihara, H. Tanaka and T. Kimura, JP 04 29'965 (31. Jan. 1992), assigned to Katakura Chikkarin Co., Ltd. For an abstract see CA 117 (1992) 48120a.

    Google Scholar 

  55. T. Sugimoto, T. Kokubo, J. Miyazaki, S. Tanimoto and M. Okano, Bioorg. Chem. 10 (1981) 311.

    Article  CAS  Google Scholar 

  56. S. Colonna, S. Banfi, F. Fontana and M. Sommaruga, J. Org. Chem. 50 (1985) 769.

    Article  CAS  Google Scholar 

  57. T. Sugimoto, T. Kokubo, Y. Matsumura, J. Miyazaki, S. Tanimoto and M. Okano, Bioorg. Chem. 10 (1981) 104.

    Article  CAS  Google Scholar 

  58. R. Annunziata, S. Banfi and S. Colonna, Tetrahedron Lett. 26 (1985) 2471.

    Article  CAS  Google Scholar 

  59. S. Colonna and A. Manfredi, Tetrahedron Lett. 27 (1986) 387.

    Article  CAS  Google Scholar 

  60. M.E. Wilson and G.M. Whitesides, J. Am. Chem. Soc. 100 (1978) 306.

    Article  CAS  Google Scholar 

  61. H. Alper and N. Hamel, J. Chem. Soc., Chem. Commun. (1990) 135.

    Google Scholar 

  62. T. Kokubo, T. Sugimoto, T. Uchida, S. Tanimoto and M. Okano, J. Chem. Soc., Chem. Commun. (1983) 769.

    Google Scholar 

  63. B. Pispisa, G. Paradossi, A. Palleschi and A. Desideri, J. Phys. Chem. 92 (1988) 3422; B. Pispisa, A. Palleschi and G. Paradossi, J. Mol. Catal. 42 (1987) 269; and references cited therein.

    Article  CAS  Google Scholar 

  64. L. Verbit, T. R. Halbert and R.B. Patterson, J. Org. Chem. 40 (1975) 1649.

    Article  CAS  Google Scholar 

  65. W.H. Pirkle and P.L. Rinaldi, J. Am. Chem. Soc. 99 (1977) 3510.

    Article  CAS  Google Scholar 

  66. V.A. Pavlov, N.I. Spitsyna and E.I. Klabunovskii, Izv. Akad. Nauk SSSR, Ser. Khim. (1983) 1653, English translation p. 1501.

    Google Scholar 

  67. H. Danda, Synlett (1991) 263.

    Google Scholar 

  68. Y. Becker, A. Elgavi and Y. Shvo, GB 2'227'429 (5. Dec. 1988), assigned to Bromine Compounds LTd.

    Google Scholar 

  69. R. Selke, K. Häupke and H.W. Krause, J. Mol. Catal. 56 (1989) 315.

    Article  CAS  Google Scholar 

  70. F.R. Hartley, Supported metal complex catalysts, in: F.R. Hartley (Ed.), The Chemistry of Metal-Carbon Bond, John Wiley & Sons Ltd, Vol. 4, p. 1163, (1987).

    Google Scholar 

  71. J. Hetflejs, Stud. Surf. Sci. Catal. 27 (1986) 497–515.

    Article  CAS  Google Scholar 

  72. J.K. Stille., Organic Synthesis via Polymer-supported Transition Metal-Catalysts. Reactive Polymers 10 (1989) 165.

    Article  Google Scholar 

  73. T. Matsuda and J.K. Stille, J. Am. Chem. Soc. 100 (1978) 268.

    Article  Google Scholar 

  74. G.L. Baker, S.J. Fritschel and J.K. Stille, J. Org. Chem. 46 (1981) 2960.

    Article  CAS  Google Scholar 

  75. R. Deschenaux and J.K. Stille, J. Org. Chem. 50 (1985) 2299.

    Article  CAS  Google Scholar 

  76. A. Corma, M. Iglesias, C. del Pino and F. Sanchez, J. Chem. Soc., Chem. Commun. (1991) 1253.

    Google Scholar 

  77. A. Corma, M. Iglesias, C. del Pino and F. Sanchez, J. Organomet. Chem. 431 (1992) 233.

    Article  CAS  Google Scholar 

  78. A. Corma, M. Iglesias, M.V. Martin, J. Rubio and F. Sanchez, Tetrahedron: Asymmetry 3 (1992) 845.

    Article  CAS  Google Scholar 

  79. B. Pugin and M. Müller, in: M. Guisnet et al. (Ed.), Heterogeneous Catalysis and Fine Chemicals III, Stud. Surf. Sci. and Cat., 78 (1993) 107.

    Google Scholar 

  80. B.L. Booth, G.C. Ofunne, C. Stacey and P.J.T. Tait, J. Organomet. Chem., 315 (1986) 142.

    Article  Google Scholar 

  81. W. Dumont, J.C. Poulin, P.T. Dang and H.B. Kagan, J. Am. Chem. Soc. 95 (1973) 8295.

    Article  CAS  Google Scholar 

  82. J.M.J. Frechet, G.D. Darling, S. Itsuno, P.-Z. Lu, V. de Meftahi and W.A. Rolls, Pure & Appl. Chem., 60 (1988) 353.

    Article  CAS  Google Scholar 

  83. J. Lieto, D. Milstein, R.L. Albright, J. V. Minkiewicz and B.C. Gates, Chemtech (1983).

    Google Scholar 

  84. H. Engelhardt and P. Orth, J. Liqu. Chromatogr., 10 (1987) 1999.

    Article  CAS  Google Scholar 

  85. M. Cerny, Coll. Czechoslov. Chem. Commun., 42 (1977) 3069.

    Article  CAS  Google Scholar 

  86. U. Nagel and E. Kinzel, J. Chem. Soc., Chem. Commun. (1986) 1098.

    Google Scholar 

  87. S. Itsuno, S. Yoshiki, I. Kiochi, M. Toshihiro, N. Seiichi and J.M.J. Frechet, J. Org. Chem. 55 (1990) 304.

    Article  CAS  Google Scholar 

  88. T. Hayashi, Tetrahedron Lett. 21 (1980) 80.

    Google Scholar 

  89. K.J. Stille, J. Macromol. Sci.-Chem. A21 (1984) 1689.

    CAS  Google Scholar 

  90. U. Nagel, H. Menzel, P.W. Lednor, W. Beck, A. Guyot and M. Bartholin, Z. Naturforsch. B: Anorg. Chem., Org. Chem., 36B (1981) 578.

    CAS  Google Scholar 

  91. K. Achiwa, Heterocycles 9 (1978) 1539.

    Article  CAS  Google Scholar 

  92. K. Achiwa, Chem. Lett. 8 (1978) 905.

    Article  Google Scholar 

  93. G.L. Baker, S.J. Fritschel and J.R. Stille, J. Org. Chem. 46 (1981) 2954.

    Article  CAS  Google Scholar 

  94. K.B. Moon and K.B. Sharpless, Tetrahedron Lett. 31 (1990) 3003.

    Article  Google Scholar 

  95. R. Selke and M. Capka, J. Mol. Catal. 63 (1990) 319.

    Article  CAS  Google Scholar 

  96. I. Toth and B.E. Hanson, J. Mol. Catal. 71 (1992) 365.

    Article  CAS  Google Scholar 

  97. N. Ishizuka, M Togashi, M. Inoue and S. Enomoto, Chem. Pharm. Bull. 35 (1987) 1686.

    Article  CAS  Google Scholar 

  98. H. Brunner, E. Bielmeier and J. Wiehl, J. Organomet. Chem. 384 (1990) 223.

    Article  CAS  Google Scholar 

  99. M. Inoue, K. Ohta, N. Ishizuka and S. Enomoto, Chem. Pharm. Bull. 31 (1983) 3371.

    Article  CAS  Google Scholar 

  100. M. Mazzei, W. Marconi and M. Riocci, J. Mol. Catal. 9 (1980) 381.

    Article  CAS  Google Scholar 

  101. J. Kaschig, European Patent 0,252,994, Al, 1988; Chem. Abstr., (1988) 109, 55454a. see also: G. Zassinovich, G. Mestroni and S. Gladiali, Chem. Rev. 92 (1992) 1051.

    Google Scholar 

  102. G. Parrinello and J.K. Stille, J. Am. Chem. Soc. 109 (1987) 7122.

    Article  CAS  Google Scholar 

  103. J.K. Stille, H. Su, G. Parrinello and L.S. Hegedus, Organometallics 10 (1991) 1183.

    Article  CAS  Google Scholar 

  104. Y. Gao, R.M. Hanson, J.M. Klunder, S.Y. Ko, H. Masamune and K.B. Sharpless, J. Am. Chem. Soc. 109 (1987) 5765.

    Article  CAS  Google Scholar 

  105. K B. Sharpless, W. Amberg, Y.L. Bennani, G.A. Crispino, J. Hartung, K.-S. Jeong, H.-L. Kwong, K. Morikawa, Z.-M. Wang, D. Xu and X.L. Zhang, J. Org. Chem. 57 (1992) 2768.

    Article  CAS  Google Scholar 

  106. S. Itsuno, Y. Sakurai, K. Ito and A. Hirao, Polymer 28 (1987) 1005.

    Article  CAS  Google Scholar 

  107. S. Itsuno, K. Ito, T. Maruyama, N. Kanda, A. Hirao and S. Nakahama, Bull. Chem. Soc. Jpn. 59 (1986) 3329.

    Article  CAS  Google Scholar 

  108. S. Itsuno and J.M.J. Frechet, J. Org. Chem. 52 (1987) 4140.

    Article  CAS  Google Scholar 

  109. G. Parrinello, R. Deschenaux and J.K. Stille, J. Org. Chem. 51 (1986) 4189.

    Article  CAS  Google Scholar 

  110. S.A. Matlin, W.J. Lough, L. Chan, D.M.H. Abram and Z. Zhou, J. Chem. Soc., Chem. Commun. (1984) 1038.

    Google Scholar 

  111. M P. Doyle, M.Y. Eismont, D.E. Bergbreiter and H.N. Gray, J. Org. Chem. 57 (1992) 6103.

    Article  CAS  Google Scholar 

  112. C. Rosini, L. Franzini, A. Raffaelli and P. Salvadori, Synthesis (1992) 503.

    Google Scholar 

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Blaser, HU., Pugin, B. (1995). Scope and Limitations of the Application of Heterogeneous Enantioselective Catalysts. In: Jannes, G., Dubois, V. (eds) Chiral Reactions in Heterogeneous Catalysis. Springer, Boston, MA. https://doi.org/10.1007/978-1-4615-1909-6_5

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